Water-insoluble metat



Patented ct. i, 293% WATER-INSOLUB munch or METAL soar Ann l rm s Frederick A. Stresen-Reuter and Charles Bimpiia,

cage,

Renter, Inc., a corporation of "I'- 111., assigncrs to Fred a. Stresen- No Drawing. Application February 2d, 1938,

Serial N0. 192,882

8 Claims.

This invention relates to soap and soap manufeature and more particularly to water-insoluble In accordance with our invention we have found that novel water-insoluble soaps can be formed from an organic acid-containing liquor under the trade-mark Spefa selected from the first, second and eighth groups and a relatively small proportion of unsaponifiable (mainly sterols). A suitable liquor called Spefa employed in accordance with our invention has a specific gravity (at 15.5 C.) of about .969; an acid number of about 164.0; a saponification number of about 173.0; an ester number of about 9.4; an iodine number (Wijs) of about 148.0; and a thiocyanogen-iodine number of about 91.0, and is a refined mixture of fatty acids,. rosin acids and sterols derived from the liquor from the sulfate-process treatment of woods such as pine.

A typical analysis of this liquor is as follows. the following analysis and in all examples hereinafter set iorth, the term parts indicates parts by weight.

for example, with aqueous caustic soda or potash,

)1 with an organic amine compound such as triathanolamine, to form a wateresoluble soap sove diluted suitably to about 20% solids in the ase of sodium or potassium soaps,- and to about solids in the case of the triethanolamine soap solution so formed may then manner, washed with boiling water and then slowly heated to about 350 F. to remove substantially all of the water therefrom.

The zinc and iron soaps embodying our invention may also be prepared by directly fusing the liquor with zinc and/or iron compounds such as the zinc and/or iron oxides or hydroxides. Thus, in accordance with our invention, the liquor may be heated to about 350 to 400 F. and the oxide or hydrate of the desired metal or mixture of metals slowly added. The mixture is 7 held at about 400 F. or higher until the reaction is complete, as indicated by the formation amount of the reaction product is dropped onto a glass slide.

In generaL. equivalent or stoichiometrical or other desirable amounts of the reactants are emsoaps such as copper and iron soaps, copper and zinc soaps, etc.

The following examples illustrate the methods employed in accordance with our invention to produce our novel water-insoluble copper, zinc and iron soaps.

DOUBLE DECOMPOSITION METHODS EXAMPLE 1 7 Part I 100 parts of the liquor Spefa are mixed with 100 parts of water and 12.38 parts of sodium hydroxide in a suitable vessel. The mixture is boiled until the resulting water-soluble soap solution has a pH of about 8 to 9; the time of reaction being about three hours. The soap solution so formed is now diluted, suitably to about solids content.

Part II soap solution produced in I is then mixed with 25.39

The water-soluble accordance with Part 20% solids) at about 200 F. The water-insoluble zinc soap is formed by double decomposition and precipitates to the bottom of the vessel. The precipitated zinc soap is washed several times 7 parts of zinc sulphate in aqueous solution (about 'withboiling, water as'by stirringand decanting anyimpurlties therefromand is'then form a dehyfio , described in Part lfitlparts of a suitable vesselto about 35D 7 about 1255 parts of zinc oxide; are

added. The mixture is. held at about 400 F.

h to remove slowlyheated,

' drated water-1nsolul:nle zinc soap.

of, ferric chloride to about 350 F. to

Exmrrr. 2

II of Example 1. FUSION METHOD,

ExAMeLE 3 v the liquor Spefa solids) to, form v The soap is then or higherv until all of the zinc oxide has re-.-

' acted with the'liquor, asindicated by'the forma tion of a clear pillon a glass slide.

The water-insoluble metal soaps embodying our invention may have an unusually high metal con-v tent whichmay c osely approximate theoretical. Using the woodfatty :acids such as the. liquor Speia in accordance with our'invention,

it is possible to obtain by the fusionmethod a zinc or iron soap havingahigher metal content than is capable of being obtained by fusing zinc or iron compoundswith rosin acids or with linseed and like fatty,acids.

, kerosene, kerosene, V. M.

- The water-insoluble metalsoaps embodying 1 our invention are readily v v v v soluble in suitable vehicles or :solventssuch as, for example, the light petroleum distillates including heavy i thepetroleum naphtha thinner sold in the tradeunder the trademark the like; or in raw or bodied vegetable drying or semi-drying oils such as, for example, linseed, perilla, China-wood oil, soy bean,

oiticica, the like; and in animal oils such as fish oils and the like. The solutions formed are homogeneous and relatively stable, and the water-insoluble soap will not, in general, readily settle out from the vehicle even when the solution is cooled to below room temperature. The water-insoluble soaps embodying our invention are more stable in solution than the corresponding soap of linseed, oleic or like fatty acids as in the prior art. The water-insoluble soaps embodying. our invention will not oxidize when in solution.

In general, the water-insoluble soaps embodying our invention are relatively odorless and are especially adapted for use in varnishes, paints,

printing inks, and the like. The Zinc soaps produced in accordance with our invention have special utility in paints to prevent wrinkling of the coating. The iron soap is an excellent drier especially in baking blacks, varnishes and enamels. It has better drying characteristics than any of the known iron soaps containing an equivalent amount of metal. The copper soaps have fungicidal properties, and being readily soluble in petroleum thinners, are especially suitable for use in paints for coating ship bottoms.

In accordance with our invention we have also produced excellent water-insoluble soaps by reacting compounds of the above metals with the liquor Spefa which has been freed from all unsaponifiable materials as, for example, by washing the water-soluble soap of petroleum ether. We have prepared also excellent water-insoluble soaps by the aid of syniron soapy our invention may,

are heated in f such as Indusoil, Liqro 400 F. and h then slowly: 1". As a new reaction produchawater-insoluble calculated as a sterol.

acids, a minor proportion of rosin small proportion of naphtha. calculated as and P. naphtha, andi and I thetic. preparations of acids, either with or without ,saponiiiables such as sterol or {sterol compounds, which closely approximate the acids, in

character and in amount, present in the liquor Spefa. Thus, we have otained: satisfactory soaps by reacting, in the manner described above, compounds of the above metals with amixture of acids, the major proportion of saturated fatty acids and the minor proportion oiwhichiis rosin ,or rosin jacidsand the like. The

synthetic acid mixture used in accordance with if desired, contain a small:

proportion ofsterol and/or sterol compounds or like unsaponiflable materials.

Wood organic may be used in lieu acid mixtures similar to SpefaE of the Spefa in accordance with our invention. 7

We claim:

coppersoap comprising acids, a minor proportion of rosin acids and a small proportion, of an unsaponifiabl'e material of a product derived frompine wood awater-insoluble zinc soap of a'product derived irompine wood comprising a 2. As a new reaction product,

I acids and a small proportionoi an 'unsaponiflable material calculated as a sterol.

20 amajor proportion of unsaturated 3 major proportion of I unsaturated i i 3. As a. new reaction product, a water-insoluble iron soapof a product derived ,irom :pine wood comprising a major proportion of unsaturated acids, afminor proportion of rosin acids and a an unsaponifiable material a sterol.

4. The method: of forming a water-insoluble soap comprising reacting a product :derived from pine'wood comprising a major proportion o'iunsaturated acids, a minor i proportion of an unsaponifiable ma-,

and a small I terial' calculated as a'sterol with relatively high temperature.

5. The method of forming a water-insoluble soap comprising reacting a product derived from pine wood comprising a major proportion of unsaturated acids, a minor proportion of rosin acids and a small proportion of an unsaponifiable material calculated as a sterol with zinc oxide at a temperature in the order of about 350 to 400 F.

6. A water-insoluble soap comprising the reaction product of a compound of.a metal selected from the class consisting of copper, zinc and iron and a mixture comprising a major proportion of unsaturated fatty acids, 2. minor proportion of rosin acids and a small proportion of a non-saponifiable material calculated as a sterol.

'7. A water-insoluble soap comprising the reaction product of a compound of a metal selected from the class consisting of copper, zinc and iron and an organic acid mixture derived from wood comprising a major proportion of unsaturated fatty acids a minor proportion of rosin acids and a small proportion of non-saponifiable material calculated as a sterol.

8. A water-insoluble soap comprising the reaction product of a compound of a metal selected from the class consisting of copper, zinc and iron and an-organic acid mixture derived from pine Wood comprising a major proportion of unsaturated fatty acids, a minor proportion of rosin acids and a small proportion of sterols.

zinc oxide at a FREDERICK A. STRESEN-REUTER. CHARLES RINIPILA. 

